Pyrazolyl acrylic acid derivatives, intermediates thereto, and in their use as microbicides

ABSTRACT

Compounds of the formula ##STR1## wherein R 1  is hydrogen or methyl, 
     R 2  is hydrogen, halogen, OCH 3 , SCH 3  or CN, 
     R 3 , R 4 , R 5  are each independently of one another hydrogen, halogen, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, C 2  -C 5  alkoxycarbonyl, C 1  -C 5  alkanoyl, C 1  -C 4  haloalkyl, C 1  -C 4  haloalkoxy, CN, NO 2 , or wherein two of those substituents are adjacent to each other and together are a methylenedioxy or difluoromethylenedioxy radical, 
     K, L, M are each independently of one another CH or N (=nitrogen atom), but at least one of these three substituents is N, and 
     Y is oxygen or sulfur, 
     are effective microbicides for controlling fungal diseases. They can be used for plant protection by themselves or as formulated compositions.

The present invention relates to a compound of formula I ##STR2##wherein R₁ is hydrogen or methyl,

R₂ is hydrogen, halogen, OCH₃, SCH₃ or CN,

R₃, R₄, R₅ are each independently of one another hydrogen, halogen, C₁-C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₅ alkoxycarbonyl, C₁ -C₅ alkanoyl, C₁ -C₄haloalkyl, C₁ -C₄ haloalkoxy, CN, NO₂, or wherein two of thesesubstituents are adjacent to each other and together are amethylenedioxy or difluoromethylenedioxy radical,

K, L, M are each independently of one another CH or N (=nitrogen atom),but at least one of these three substituents is N, and

Y is oxygen or sulfur.

The compounds of the invention have fungicidal properties and aresuitable fungicides especially for use in agriculture and horticulture.

The invention further relates to a process for the preparation of thenovel compounds, to fungicidal compositions that contain such compoundsas active ingredients, as well as to the use of such compounds andcompositions for controlling phytopathogenic fungi.

In the narrower sense, the invention relates to a compound of formula I,wherein R₁, R₂, K, L, M and Y have the given meanings and R₃, R₄, R₅ areeach independently of one another hydrogen, halogen, C₁ C₄ alkyl, C₁ -C₄alkoxy, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, CN, NO₂, or wherein two ofthese substituents are adjacent to each other and together are amethylenedioxy or difluoromethylenedioxy radical.

In formula I above and throughout this specification, alkyl, haloalkyl,haloalkoxy or alkoxy groups, depending on the number of carbon atoms,are straight-chain or branched. Alkyl is methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. The C₂ -C₅alkoxycarbonyl substituent is comprised of a C₁ -C₄ alkoxy group and acarbonyl group.

Halogen by itself or as moiety of an alkyl or alkoxy group is fluoro,chloro, bromo or iodo.

If the compounds of formula I contain asymmetrical carbon atoms, thenthe compounds are obtained in optically active form. Solely owing to thepresence of the aliphatic double bond the compounds are obtained at allevents in the [E] or [Z] form. Atropisomerism can also occur. All thepossible isomeric forms as well as mixtures thereof, for example racemicmixtures and any form of [E/Z] mixtures, are embraced by formula I.

An important group of compounds falling within the scope of formula Iembraces those compounds wherein one of the substituents K, L or M isnitrogen and the others are both CH, wherein R₂ is hydrogen or halogen,and the substituents R₁, R₃, R₄, R₅ and Y have the given meanings(subgroup IA), and, among these, preferably those compounds wherein K isnitrogen, L and M are CH and R₁ is methyl (subgroup Ia).

A further important group of compounds falling within the scope offormula I embraces those compounds wherein two of the substituents K, Land M are nitrogen, and the third substituent is CH, and the remainingsubstituents have the given meanings (subgroup IB) and, among these,preferably those compounds wherein K is CH and L and M are nitrogen, R₁is methyl, R₄ is hydrogen and R₂, R₃, R₅ and Y have the given meanings(subgroup IBB).

Within this last mentioned group of pyrimidine derivatives IBB, thosecompounds are preferred wherein R₂ is hydrogen or halogen, Y is oxygenand R₃ and R₅ are each independently of the other hydrogen, halogen,methyl, ethyl, methoxy, ethoxy, CF₃, OCF₃, OCHF₂, NO₂ or CN, or bothadjacent to each other are a methylenedioxy or difluoromethylenedioxyradical (subgroup Ib).

A further group of compounds falling within the scope of formula Iembraces 1,3,5-triazinyl derivatives, i.e. those compounds wherein thesubstituents K, L and M are nitrogen, and Y and R₁ to R₅ have the givenmeanings (subgroup IC), preferably those compounds wherein R₁ is methyl,R₄ is hydrogen, Y is oxygen and R₂, R₃ and R₅ have the given meanings(subgroup ICC).

Within this last mentioned group ICC, those compounds are preferredwherein R₂ is fluoro, chloro, bromo, OCH₃, SCH₃ or CN, and R₃ and R₅ areeach independently of the other hydrogen, halogen, methyl, ethyl,methoxy, ethoxy, CF₃, OCF₃, OCHF₂, NO₂ or CN, or both adjacent to eachother are a methylenedioxy or difluoromethylenedioxy radical (subgroupIc).

Among the biologically preferred individual compounds of subgroup IBBare the compounds 1.1, 1.3, 1.5, 1.13, 1.28, 1.41, 1.52 and 1.67 listedin Table 1.

The process of this invention for the preparation of the novel compoundsof formula I comprises reacting a pyrazolyl acetate derivative offormula V ##STR3## wherein R₁ to R₅, Y, K, L and M are as defined forformula I in basic medium, with methyl formate, and methylating the3-hydroxyacrylate so obtained. Suitable methylating reagents includemethyl iodide, dimethyl sulfate, diazomethane and the like.

The invention relates likewise to the novel pyrazolyl acetates offormula V, wherein

R₁ is hydrogen or methyl,

R₂ is hydrogen, halogen, OCH₃, SCH₃ or CN,

R₃, R₄, R₅ are each independently of one another hydrogen, halogen, C₁-C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₅ alkoxycarbonyl, C₁ -C₅ alkanoyl, C₁ -C₄haloalkyl, C₁ -C₄ haloalkoxy, CN, NO₂, or wherein two of thesesubstituents are adjacent to each other and together are amethylenedioxy or difluoromethylenedioxy radical,

K, L, M are each independently of one another CH or N, but at least oneof the three substituents is N, and

Y is oxygen or sulfur;

as well as to a process for the preparation of said compounds of formulaV, which comprises reacting a (4-hydroxypyrazol-5-yl)methyl acetatederivative of formula III ##STR4## wherein R₁ is hydrogen or methyl,either a) with a heterocyclylphenyl(thio)ether of formula VII ##STR5##or b) initially with a heterocyclic compound of formula VIII ##STR6## togive an intermediate of formula IV ##STR7## and reacting saidintermediate with a (thio)phenol derivative of formula IX ##STR8## inwhich formulae VII, VIII, IV and IX above the substituents R₁ to R₅, Y,K, L and M are as defined for formula V, while U and V in formulae IV,VII and VIII are a leaving group, preferably chloro, bromo, iodo,mesyloxy, benzenesulfonyloxy or tosyloxy.

Both process steps a) and b) can be carried out in inert solvents,conveniently in the presence of a base. The reaction temperature is inthe range from -20° C. to the boiling temperature of the solvent, thepreferred range being from 0° C. to 150° C.

Illustrative examples of suitable inert solvents are: aliphatic andaromatic unsubstituted or halogenated hydrocarbons such as pentane,hexane, heptane, cyclohexane, petroleum ether, petroleum spirit,ligroin, benzene, toluene, methylene chloride, ethylene chloride,chloroform, carbon tetrachloride, chlorobenzene, o-dichiorobenzene; alsoethers, including diethyl and dibutyl ether, glycol dimethyl ether anddiglycol dimethyl ether, tetrahydrofuran and dioxane; ketones, typicallyacetone, methyl ethyl ketone, methyl isopropyl ketone and methylisobutyl ketone; nitriles, including acetonitrile and propionitrile,benzonitrile, glutarodinitrile; amides, typically dimethyl formamide,dimethyl acetamide and N-methylpyrrolidone; as well as dimethylsurfoxide, tetramethylensulfone and hexamethylphosphoric triamide. It isalso possible to use mixtures of the aforementioned solvents.

Suitable bases typically include: hydroxides, hydrogencarbonates,carbonates and alcoholates of alkali metals and alkaline earth metals(Li, Na, K, Ca, Mg), sodium hydride, tertiary amines such astrimethylamine, triethylamine, pyridine, picolines, N-methylmorpholine,N-ethylpyrrolidine, diazabicyclo(4,3,0)undecane (DBU),1,4-diazabicyclo-2,2,2-octane (DABCO), diazabicyclo(3,2,0)nonane (DBN).

Silver oxide may also be used as weakly catalytic base.

The novel compounds of formula I can be prepared in accordance with thefollowing synthesis scheme 1: ##STR9##

The compounds of formula I so obtained can be isolated and purified bymethods that are known per se. Mixtures of isomers, for example mixturesof E/Z isomers, can likewise be separated by per se known methods intothe pure isomers, typically by chromatography or fractionalcrystallisation.

The 4-hydroxypyrazolylmethyl acetate of formula III can be obtained bythe method disclosed in EP-A-483 851 by hydrogenation of thecorresponding 4-benzyl ether. This 4-benzyl ether can be obtained by themethod disclosed in EP-A-433 899 (for the preparation of the startingmaterials of "formula IIb" as defined therein).

Illustrative examples of solvents which may suitably be used for thishydrogenation are hydrocarbons such as toluene, benzene, xylene,petroleum ether etc.; esters such as ethyl acetate etc.; carboxylicacids such as glacial acetic acid, formic acid etc.; alcohols such asmethanol, ethanol, glycol etc.; ethers such as diethyl ether, dioxane,tetrahydrofuran etc. The presence of palladium/carbon as catalyst forspeeding up the reaction is advantageous. The reaction temperature is inthe range from 0° C. to the boiling temperature of the solvent,preferably in the range from room temperature to 70° C.

Compounds of formula I can also be prepared by a process analogous tothat of synthesis scheme 1, wherein the acetate radical in formula II ispresent from the start in the methoxyacrylate radical (EP-A1-433 899,page 6 et seq.).

The invention also relates to the novel intermediate of formula III##STR10## wherein R₁ is hydrogen or methyl.

It has been found that the compounds of formula I have, for practicalpurposes, a particularly advantageous microbicidal spectrum forcontrolling phytopathogenic micro-organisms, especially fungi. They havevery useful curative, preventive and, in particular, systemicproperties, and are used for protecting numerous cultivated plants. Thecompounds of formula I can be used to inhibit or destroy the pests whichoccur on plants or parts of plants (fruit, blossoms, leaves, stems,tubers, roots) in different crops of useful plants, while at the sametime the parts of plants which grow later are also protected from attackby phytopathogenic microorganisms.

The compounds of formula I can also be used as dressing agents forprotecting seeds (fruit, tubers, grains) and plant cuttings againstfungal infections as well as against phytopathogenic fungi which occurin the soil.

The compounds of formula I are effective against the phytopathogenicfungi belonging to the following classes: Fungi imperfecti (inparticular Botrytis and also Pyricularia, Helminthosporium, Fusarium,Septoria, Cercospora, Cercosporella and Alternaria); Basidiomycetes(e.g. Rhizocotonia, Hemileia, Puccinia). They are also effective againstthe class of the Ascomycetes (e.g. Venturia and Erysiphe, Podosphaera,Monilinia and Uncinula), and especially against that of the Oomycetes(e.g. Phytophthora, Peronospora, Bremia, Pythium, Plasmopara).

Target crops suitable for the plant protective utility disclosed hereintypically comprise within the scope of the present invention thefollowing species of plants: cereals (wheat, barley, rye, oats, rice,maize, sorghum and related species), beet (sugar beet and fodder beet),pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds,cherries, strawberries, gooseberries, raspberries and blackberries),leguminous plants (beans, lentils, peas, soybeans), oil plants (rape,mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoabeans, groundnuts), cucumber plants (cucumber, marrows, melons), fibreplants (cotton, flax, hemp, jute), citrus fruit (oranges, lemons,grapefruit, mandarins), vegetables (spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes, sweet peppers), lauraceae(avocados, cinnamon, camphor), or plants such as tobacco, nuts, coffee,sugar cane, tea, pepper, vines, hops, egg-plants, bananas and naturalrubber plants, as well as ornamentals.

The compounds of formula I are usually applied in the form ofcompositions and can be applied to the crop area or plant to be treated,simultaneously or in succession, with further compounds. These furthercompounds can be fertilisers or micronutrient donors as well as otherother preparations that influence plant growth. It is also possible inthis connection to use selective herbicides, insecticides, fungicides,bactericides, nematicides, mollusicides or mixtures of several of thesepreparations, together with optional carriers, surfactants orapplication-promoting adjuvants commonly employed in the art offormulation.

Suitable carriers and adjuvants may be solid or liquid and correspond tothe appropriate substances ordinarily employed in formulationtechnology, including natural or regenerated mineral substances,solvents, dispersants, wetting agents, tackifiers, thickeners, bindersor fertilisers.

Suitable solvents are: aromatic hydrocarbons, the fractions containing 8to 12 carbon atoms, typically xylene mixtures or substitutednaphthalenes, phthalates such as dibutyl or dioctyl phthalate, aliphatichydrocarbons such as cyclohexane or paraffins; also alcohols and glycolsand their ethers and esters, such as ethanol, ethylene glycol, ethyleneglycol monomethyl or monoethyl ether, ketones such as cyclohexanone,strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethyl formamide, as well as vegetable oils or epoxidisedvegetable oils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers typically used for dusts and dispersible powders areusually natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite.

Further especially useful application-promoting adjuvants that may leadto a reduction of the concentration of active ingredient are natural(animal or vegetable) or synthetic phospholipids of the series of thecephalins and lecithins which can conveniently be isolated fromsoybeans.

Depending on the nature of the compound of formula I to be formulated,suitable surface-active compounds are nonionic, cationic and/or anionicsurfactants having good emulsifying, dispersing and wetting properties.The term "surfactants" will also be understood as comprising mixtures ofsurfactants.

Suitable anionic surfactants can be water-soluble soaps as well aswater-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orammonium salts or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), typically the sodium or potassium salts of oleic or stearic acid,or of natural fatty acid mixtures which can be obtained, inter alia,from coconut oil or tallow oil. Further suitable surfactants are alsothe fatty acid methyltaurin salts.

Nonionic surfactants are polyglycol ether derivatives of aliphatic orcycloaliphatic alcohols, or saturated or unsaturated fatty acids andalkylphenols, said derivatives containing 3 to 30 glycol ether groupsand 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to18 carbon atoms in the alkyl moiety of the alkylphenols.

Typical examples of nonionic surfactants arenonylphenolpolyethoxyethanols, castor oil polyglycol ethers, adducts ofpolypropylene and polyethylene oxide, tributylphenoxypolyethhoxyethanol,polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan are also suitable nonionicsurfactants, typically polyoxyethylene sorbitan trioleate.

Cationic surfactants are preferably quaternary ammonium salts carrying,as N-substituents, at least one C₈ -C₂₂ alkyl radical and, as furthersubstituents, optionally halogenated lower alkyl, benzyl orhydroxy-lower alkyl radicals.

The anionic, nonionic or cationic surfactants customarily employed informulation technology are familiar to those skilled in the an or may befound in the relevant literature.

"Mc Cutcheon's Detergents and Emulsifiers Annual", Mc Publishing Corp.,Glen Rock, N.J., 1988.

M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, ChemicalPublishing Co., New York, 1980-1981.

Dr. Helmut Stache "Tensid-Taschenbuch" (Handbook of Surfactants), CarlHanser Verlag, Munich/Vienna 1981.

The agrochemical compositions usually contain 0.1 to 99% by weight,preferably 0.1 to 95% by weight, of a compound of formula I, 99.9 to 1%by weight, preferably 99.9 to 5% by weight of a solid or liquidadjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of asurfactant.

Whereas commercial products will preferably be formulated asconcentrates, the end user will normally use formulations diluted toconcentrations down to 0.0001%.

The compositions may also contain further ingredients such asstabilisers, antifoams, viscosity regulators, binders, tackifiers aswell as fertilisers or other chemical agents to obtain special effects.

The formulations, i.e. the compositions, preparations or mixturescontaining the compound of formula I and, where appropriate, a solid orliquid adjuvant, are prepared in known manner, conveniently byhomogeneously mixing and/or grinding the active ingredient withextenders, as with a solvent (mixture), a solid carrier and, in somecases, surface-active compounds (surfactants).

A preferred method of applying a compound of formula I, or anagrochemical composition which contains at least one of said compounds,is foliar application. The frequency of application and the rate ofapplication will depend on the risk of infestation by the correspondingpathogen. However, the compound of formula I can also penetrate theplant through the roots via the soil (systemic action) by drenching thelocus of the plant with a liquid formulation, or by applying thecompounds in solid form to the soil, e.g. in granular form (soilapplication). In crops of water rice such granulates can be applied tothe flooded rice field. The compounds of formula I may also be appliedto seeds (coating) by impregnating the seeds either with a liquidformulation of the fungicide or coating them with a solid formulation.In principle, any kind of plant propagation material can be protectedwith compounds of formula I, e.g. seeds, roots or stems.

The compounds of formula I are used in unmodified form or, preferably,together with the adjuvants conventionally employed in the art offormulation. To this end they are conveniently formulated in knownmanner to emulsifiable concentrates, coatable pastes, directly sprayableor dilutable solutions, dilute emulsions, wettable powders, solublepowders, dusts, granulates, and also encapsulations in polymericsubstances. As with the type of the compositions, the methods ofapplication, such as spraying, atomising, dusting, scattering, coatingor pouring, are chosen in accordance with the intended objectives andthe prevailing circumstances. Advantageous rates of application arenormally from 10 g to 2 kg of active ingredient (a.i.) per hectare,preferably from 25 g to 800 g a.i./ha. For use as seed dressing agents,advantageous rates of application are from 0.001 g to 1.0 g activeingredient per kg of seeds.

The invention is illustrated in more detail by the followingnon-limitative Examples.

EXAMPLE P1

a) Preparation of the intermediate of formula III

Methyl (1,3-dimethyl-4-hydroxypyrazol-5-yl)acetate:

A solution of 10.3 g (37.5 mmol) of methyl(4-benzyloxy-1,3-dimethylpyrazol-5-yl)acetate in 200 ml of methanol ishydrogenated in the presence of 1 g of 10% Pd/C. When the reaction iscomplete, the reaction mixture is filtered and the filtrate isconcentrated under vacuum. The residue is recrystallised fromdichloromethane/n-hexane, giving methyl(1,3-dimethyl-4-hydroxypyrazol-5-yl)acetate; m.p. 119°-120° C.

b) Preparation of the intermediate of formula V

Methyl{1,3-dimethyl-4-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]pyrazol-5-yl}acetate:

To a solution of 3.0 g (16.3 mmol) of methyl(1,3-dimethyl-4-hydroxypyrazol-5-yl)acetate in 80 ml of dimethylformamide are added 6.9 g (50.0 mmol) of potassium carbonate and 2.7 g(18.0 mmol) of 4,6-dichloropyrimidine. After stirring for 3 hours atroom temperature, 2.2 g (20.0 mmol) of 2-fluorophenol are added andstirring is continued for 3 hours at 80°-85° C. Then 300 ml of ice-waterare added, followed by extraction with 400 ml of diethyl ether. Theorganic phase is washed with 2M sodium hydroxide solution, water andsodium chloride solution, dried and concentrated under vacuum. Theresultant brown oil is chromatographed over silica gel withtetrahydrofuran/n-hexane (1:1) as eluant, giving methyl{1,3-dimethyl-4-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]pyrazol-5-yl}acetateas a yellow resin: MS: 372 (M⁺, 80%), 312 (100).

c) Preparation of the final product

E-Methyl-2-{1,3-dimethyl-4-[6-(2-fluorophenoxy)-pyrimidin-4-yloxy]pyrazol-5-yl}-3-methoxyacrylate(compound 1.3, Table 1):

A solution of 3.5 g (9.3 mmol) of methyl{1,3-dimethyl-4-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]pyrazol-5-yl}acetateand 10 ml of methyl formate in 10 ml of dimethyl formamide is slowlyadded dropwise to a suspension of 0.5 g (20.0 mmol) of sodium hydride(95%) in 40 ml of dimethyl formamide, while keeping the temperaturebelow 30° C. The reaction mixture is stirred for 2 hours at roomtemperature, acidified with acetic acid and, after addition of 200 ml ofice-water, extracted with 200 ml of ethyl acetate. The organic phase iswashed with water and sodium chloride solution, dried and concentratedunder vacuum, givingE-methyl-2-{1,3-dimethyl-4-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]pyrazol-5-yl}-3-hydroxyacrylateas a brown resin, which is stirred together with 1.8 g (13.0 mmol) ofpotassium carbonate and 0.9 ml (6.7 mmol) of dimethyl sulfate in 40 mlof acetone for 3 hours at room temperature. The reaction mixture isfiltered, the filtrate is diluted with 50 ml of water and extracted with100 ml of ethyl acetate. The organic phase is washed with sodiumchloride solution, dried and concentrated under vacuum. The residue ischromatographed over silica gel tetrahydrofuran/n-hexane (1:1) aseluant, givingE-methyl-2-{1,3-dimethyl-4-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]pyrazol-5-yl}-3-methoxyacrylateas a yellow resin; MS: 414 (M⁺, 44%), 75 (100).

The following compounds can be prepared in this manner or according toone of the above described methods.

                                      TABLE 1                                     __________________________________________________________________________     ##STR11##                                                                    Cmpd.                                                                             R.sub.1                                                                          Y R.sub.3   R.sub.4                                                                           R.sub.5                                                                           Phys. data                                         __________________________________________________________________________    1.1 CH.sub.3                                                                         O 2-CN      H   H   mp. 114-116° C.                             1.2 CH.sub.3                                                                         O H         H   H                                                      1.3 CH.sub.3                                                                         O 2-F       H   H   MS: 414(M.sup.+, 44%), 75 (100)                    1.4 CH.sub.3                                                                         O 2-Cl      H   H   MS: 430(M.sup.+, 39%), 75 (100)                    1.5 CH.sub.3                                                                         O 2-Br      H   H   MS: 474(M.sup.+, 31%), 75 (100)                    1.6 CH.sub.3                                                                         O 2-Me      H   H   MS: 410(M.sup.+, 31%), 75 (100)                    1.7 CH.sub.3                                                                         O 2-OMe     H   H   MS: 426(M.sup.+, 53%), 395 (100)                   1.8 CH.sub.3                                                                         O 2-CF.sub.3                                                                              H   H                                                      1.9 CH.sub.3                                                                         O 2-NO.sub.2                                                                              H   H   mp. 143-145° C.                             1.10                                                                              CH.sub.3                                                                         O 3-CN      H   H   mp. 143-145° C.                             1.11                                                                              CH.sub.3                                                                         O 3-F       H   H   MS: 414(M.sup.+, 83%), 75 (100)                    1.12                                                                              CH.sub.3                                                                         O 3-Cl      H   H   MS: 430(M.sup.+, 44%), 75 (100)                    1.13                                                                              CH.sub.3                                                                         O 3-Br      H   H   MS: 474(M.sup.+, 27%), 75 (100)                    1.14                                                                              CH.sub.3                                                                         O 3-Me      H   H   MS: 410(M.sup.+, 79%), 75 (100)                    1.15                                                                              CH.sub.3                                                                         O 3-OMe     H   H   MS: 426(M.sup.+, 53%), 75 (100)                    1.16                                                                              CH.sub.3                                                                         O 3-CF.sub.3                                                                              H   H   MS: 464(M.sup.+, 74%), 75 (100)                    1.17                                                                              CH.sub.3                                                                         O 3-OCF.sub.3                                                                             H   H                                                      1.18                                                                              CH.sub.3                                                                         O 3-NO.sub.2                                                                              H   H   m.p. 173-175° C.                            1.19                                                                              CH.sub.3                                                                         O 4-CN      H   H                                                      1.20                                                                              CH.sub.3                                                                         O 4-F       H   H   MS: 414(M.sup.+, 57%), 75 (100)                    1.21                                                                              CH.sub.3                                                                         O 4-Cl      H   H   MS: 430(M.sup.+, 42%), 75 (100)                    1.22                                                                              CH.sub.3                                                                         O 4-Br      H   H   MS: 474(M.sup.+, 38%), 75 (100)                    1.23                                                                              CH.sub.3                                                                         O 4-Me      H   H   MS: 410(M.sup.+, 81%), 75 (100)                    1.24                                                                              CH.sub.3                                                                         O 4-OMe     H   H                                                      1.25                                                                              CH.sub.3                                                                         O 4-CF.sub.3                                                                              H   H                                                      1.26                                                                              CH.sub.3                                                                         O 4-OCF.sub.3                                                                             H   H                                                      1.27                                                                              CH.sub.3                                                                         O 4-NO.sub.2                                                                              H   H                                                      1.28                                                                              CH.sub.3                                                                         O 2-Et      H   H   MS: 424(M.sup.+, 100%), 75 (72)                    1.29                                                                              CH.sub.3                                                                         O 2-OEt     H   H                                                      1.30                                                                              CH.sub.3                                                                         O 3,4-methylenedioxy                                                                          H   MS: 440(M.sup.+, 100%), 75 (82)                    1.31                                                                              CH.sub.3                                                                         O 2-F       3-F H                                                      1.32                                                                              CH.sub.3                                                                         O 2-Cl      3-Cl                                                                              H                                                      1.33                                                                              CH.sub.3                                                                         O 2-Me      3-Me                                                                              H   MS: 424(M.sup.+, 42%), 75 (100)                    1.34                                                                              CH.sub.3                                                                         O 2-OMe     3-OMe                                                                             H                                                      1.35                                                                              CH.sub.3                                                                         O 3-F       5-F H                                                      1.36                                                                              CH.sub.3                                                                         O 3-Cl      5-Cl                                                                              H                                                      1.37                                                                              CH.sub.3                                                                         O 3-Me      5-Me                                                                              H   MS: 424(M.sup.+, 90%), 75 (100)                    1.38                                                                              CH.sub.3                                                                         O 3-OMe     5-OMe                                                                             H                                                      1.39                                                                              CH.sub.3                                                                         O 2-F       4-F H                                                      1.40                                                                              CH.sub.3                                                                         O 2-Me      4-Me                                                                              H   MS: 424(M.sup.+, 74%), 75 (100)                    1.41                                                                              CH.sub.3                                                                         O 2-Me      4-Cl                                                                              H   MS: 444(M.sup.+, 58%), 75 (100)                    1.42                                                                              CH.sub.3                                                                         O 3-OMe     4-OMe                                                                             5-OMe                                                  1.43                                                                              H  O 2-CN      H   H                                                      1.44                                                                              H  O H         H   H                                                      1.45                                                                              H  O 2-F       H   H                                                      1.46                                                                              H  O 2-Cl      H   H                                                      1.47                                                                              H  O 2-Br      H   H                                                      1.48                                                                              H  O 2-Me      H   H                                                      1.49                                                                              H  O 2-OMe     H   H                                                      1.50                                                                              H  O 2-CF.sub.3                                                                              H   H                                                      1.51                                                                              H  O 2-NO.sub.2                                                                              H   H                                                      1.52                                                                              CH.sub.3                                                                         S H         H   H   MS: 412(M.sup.+, 64%), 75 (100)                    1.53                                                                              CH.sub.3                                                                         S 2-Cl      H   H   m.p. 138-140° C.                            1.54                                                                              CH.sub.3                                                                         S 2-Br      H   H                                                      1.55                                                                              CH.sub.3                                                                         S 2-Me      H   H                                                      1.56                                                                              CH.sub.3                                                                         S 2-OMe     H   H   m.p. 162-164° C.                            1.57                                                                              CH.sub.3                                                                         O 3,4-difluoromethyl-                                                                         H                                                               enedioxy                                                             1.58                                                                              CH.sub.3                                                                         O 3-Et      H   H   MS: 424(M.sup.+, 58%), 75 (100)                    1.59                                                                              CH.sub.3                                                                         O 2-Cl      5-Me                                                                              H   m.p. 161-163° C.                            1.60                                                                              CH.sub.3                                                                         O 3-Cl      4-F H   m.p. 122-124° C.                            1.61                                                                              CH.sub.3                                                                         O 3-Me      4-Cl                                                                              5-Me                                                                              MS: 458(M.sup.+, 52%), 75 (100)                    1.62                                                                              CH.sub.3                                                                         O 4-Et      H   H   MS: 424(M.sup.+, 100%), 75 (38)                    1.63                                                                              CH.sub.3                                                                         O 3-Me      4-Cl                                                                              H   MS: 444(M.sup.+, 71%), 75 (100)                    1.64                                                                              CH.sub.3                                                                         O 3-Me      4-Me                                                                              H   MS: 424(M.sup.+, 60%), 75 (100)                    1.65                                                                              CH.sub.3                                                                         O 2-COOMe   H   H   MS: 454(M.sup.+, 62%), 75 (100)                    1.66                                                                              CH.sub.3                                                                         O 2-CHO     H   H   m.p. 111-115° C.                            1.67                                                                              CH.sub.3                                                                         O 2-COMe    H   H   MS: 438(M.sup.+, 100%), 75 (75)                    __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                         ##STR12##                                                                    Cmpd.  R.sub.1                                                                              Y     R.sub.3      R.sub.4                                                                           R.sub.5                                                                           Phys. data                           ______________________________________                                        2.1    CH.sub.3                                                                             O     2-CN         H   H                                        2.2    CH.sub.3                                                                             O     H            H   H                                        2.3    CH.sub.3                                                                             O     2-F          H   H                                        2.4    CH.sub.3                                                                             O     2-Cl         H   H                                        2.5    CH.sub.3                                                                             O     2-Br         H   H                                        2.6    CH.sub.3                                                                             O     2-Me         H   H                                        2.7    CH.sub.3                                                                             O     2-OMe        H   H                                        2.8    CH.sub.3                                                                             O     2-CF.sub.3   H   H                                        2.9    CH.sub.3                                                                             O     2-NO.sub.2   H   H                                        2.10   H      O     2-CN         H   H                                        2.11   H      O     H            H   H                                        2.12   H      O     2-F          H   H                                        2.13   H      O     2-Cl         H   H                                        2.14   H      O     2-Br         H   H                                        2.15   H      O     2-Me         H   H                                        2.16   H      O     2-OMe        H   H                                        2.17   H      O     2-CF.sub.3   H   H                                        2.18   H      O     2-NO.sub.2   H   H                                        2.19   CH.sub.3                                                                             S     H            H   H                                        2.20   CH.sub.3                                                                             S     2-Cl         H   H                                        2.21   CH.sub.3                                                                             S     2-Br         H   H                                        2.22   CH.sub.3                                                                             S     2-Me         H   H                                        2.23   CH.sub.3                                                                             S     2-OMe        H   H                                        2.24   CH.sub.3                                                                             O     4-Cl         H   H   oil                                  2.25   CH.sub.3                                                                             O     4-NO.sub.2   H   H                                        2.26   CH.sub.3                                                                             O     3-Me         H   H   oil                                  2.27   CH.sub.3                                                                             O     3,4-difluoromethyl-                                                                            H                                                            enedioxy                                                  ______________________________________                                    

                                      TABLE 3                                     __________________________________________________________________________     ##STR13##                                                                    Cmpd.                                                                              R.sub.1                                                                          R.sub.2                                                                          Y R.sub.3 R.sub.4                                                                         R.sub.5                                                                         Phys. data                                           __________________________________________________________________________    3.1  CH.sub.3                                                                         Cl O 2-CN    H H MS: 456(M.sup.+, 16%), 75 (100)                      3.2  CH.sub.3                                                                         Cl O H       H H                                                      3.3  CH.sub.3                                                                         Cl O 2-F     H H                                                      3.4  CH.sub.3                                                                         Cl O 2-Cl    H H                                                      3.5  CH.sub.3                                                                         Cl O 2-Br    H H                                                      3.6  CH.sub.3                                                                         Cl O 2-Me    H H                                                      3.7  CH.sub.3                                                                         Cl O 2-OMe   H H                                                      3.8  CH.sub.3                                                                         Cl O 2-CF.sub.3                                                                            H H                                                      3.9  CH.sub.3                                                                         Cl O 2-NO.sub.2                                                                            H H                                                      3.10 H  Cl O 2-CN    H H                                                      3.11 H  Cl O H       H H                                                      3.12 CH.sub.3                                                                         Cl S H       H H                                                      3.13 CH.sub.3                                                                         OMe                                                                              O 2-CN    H H                                                      3.14 CH.sub.3                                                                         OMe                                                                              O H       H H                                                      3.15 CH.sub.3                                                                         OMe                                                                              S H       H H                                                      3.16 CH.sub.3                                                                         SMe                                                                              O 2-CN    H H                                                      3.17 CH.sub.3                                                                         SMe                                                                              O H       H H                                                      3.18 CH.sub.3                                                                         SMe                                                                              S H       H H                                                      3.19 CH.sub.3                                                                         CN O 2-CN    H H                                                      3.20 CH.sub.3                                                                         CN O H       H H                                                      3.21 CH.sub.3                                                                         CN S H       H H                                                      3.22 CH.sub.3                                                                         H  O 2-CN    H H                                                      3.23 CH.sub.3                                                                         H  O H       H H                                                      3.24 CH.sub.3                                                                         H  S H       H H                                                      3.25 CH.sub.3                                                                         H  O 4-Cl    H H                                                      3.26 CH.sub.3                                                                         H  O 4-NO.sub.2                                                                            H H                                                      3.27 CH.sub.3                                                                         H  O 3-Me    H H                                                      3.28 CH.sub.3                                                                         H  O 4-Me    H H                                                      3.29 CH.sub.3                                                                         H  O 3,4-difluoro-                                                                           H                                                                   methylenedioxy                                                   __________________________________________________________________________

2. Formulation Examples for compounds of formula I (%=percentage byweight)

    ______________________________________                                        2.1. Emulsifiable concentrates                                                                   a)        b)     c)                                        ______________________________________                                        compound of Tables 1-3                                                                           25%       40%    50%                                       calcium dodecylbenzenesulfonate                                                                   5%        8%     6%                                       castor oil polyethylene glycol ether                                                              5%       --     --                                        (36 mol ethylene oxide)                                                       tributylphenyl polyethylene glycol                                                               --        12%    4                                         ether %                                                                       (30 mol ethylene oxide)                                                       cyclohexanone      --        15%    20%                                       xylene mixture     65%       25%    20%                                       ______________________________________                                    

Emulsions of any desired concentration can be prepared by diluting suchconcentrates with water.

    ______________________________________                                        2.2. Solutions      a)     b)     c)    d)                                    ______________________________________                                        compound of Tables 1-3                                                                            80%    10%    5%    95%                                   ethylene glycol monomethyl ether                                                                  20%    --     --    --                                    polyethylene glycol 400                                                                           --     70%    --    --                                    N-methyl-2-pyrrolidone                                                                            --     20%    --    --                                    epoxidised coconut oil                                                                            --     --     1%     5%                                   petroleum distillate                                                                              --     --     94%   --                                    boiling range: 160-190° C.)                                            ______________________________________                                    

These solutions are suitable for application in the form of microdrops.

    ______________________________________                                        2.3. Granulates     a)      b)                                                ______________________________________                                        compound of Tables 1-3                                                                            5%      10%                                               kaolin              94%     --                                                highly disperse silica                                                                            1%      --                                                attapulgite         --      90%                                               ______________________________________                                    

The compound is dissolved in methylene chloride, the solution is sprayedon to the carrier and the solvent is then evaporated under vacuum.

    ______________________________________                                        2.4. Dusts         a)      b)                                                 ______________________________________                                        compound of Tables 1-3                                                                           2%      5%                                                 highly disperse silica                                                                           1%      5%                                                 talcum             97%     --                                                 kaolin             --      90%                                                ______________________________________                                    

Ready-for-use dusts are obtained by intimately the carriers with thecompound.

    ______________________________________                                        2.5. Wettable powders                                                                           a)         b)     c)                                        ______________________________________                                        compound of Tables 1-3                                                                          25%        50%    75%                                       sodium ligninsulfonate                                                                          5%          5%    --                                        sodium lauryl sulfate                                                                           3%         --      5%                                       sodium diisobutylnaphthalene                                                                    --          6%    10%                                       sulfonate                                                                     octylphenol polyethylene glycol                                                                 --          2%    --                                        ether                                                                         (7-8 mol ethylene oxide)                                                      highly dispersed silica                                                                         5%         10%    10%                                       kaolin            62%        27%    --                                        ______________________________________                                    

The compound is thoroughly mixed with the adjuvants and the mixture iswell ground in a suitable mill to give wettable powders which can bediluted with water to suspensions of any desired concentration.

    ______________________________________                                        2.6 Emulsifiable concentrate                                                  ______________________________________                                        compound of Tables 1-3                                                                              10%                                                     octylphenol polyethylene glycol                                                                     3%                                                      ether                                                                         (4-5 mol ethylene oxide)                                                      calcium dodecylbenzenesulfonate                                                                     3%                                                      castor oil polyglycol ether                                                                         4%                                                      (35 mol ethylene oxide)                                                       cyclohexanone         34%                                                     xylene mixture        50%                                                     ______________________________________                                    

Emulsions of any desired concentration can be prepared by diluting thisconcentrate with water.

    ______________________________________                                        2.7. Dusts          a)      b)                                                ______________________________________                                        compound of Tables 1-3                                                                             5%      8%                                               talcum              95%     --                                                kaolin              --      92%                                               ______________________________________                                    

Ready-for-use dusts are obtained by grinding the active ingredient withthe carrier in a suitable mill.

    ______________________________________                                        2.8 Extruder granulate                                                        ______________________________________                                        compound of Tables 1-3                                                                           10%                                                        sodium ligninsulfonate                                                                            2%                                                        carboxymethyl cellulose                                                                           1%                                                        kaolin             87%                                                        ______________________________________                                    

The active ingredient is mixed with the adjuuvants, the mixture isground and moistened with water. This mixture is extruded and then driedin a stream of air.

    ______________________________________                                        2.9 Coated granulate                                                          ______________________________________                                        compound of Tables 1-3                                                                           3%                                                         polyethylene glycol 200)                                                                         3%                                                         kaolin             94%                                                        ______________________________________                                    

The finely ground compound is applied uniformly in a mixer to the kaolinwhich is moistened with polyethylene glycol to give non-dusting coatedgranulates.

    ______________________________________                                        2.10 Suspension concentrate                                                   ______________________________________                                        compound of Table 1     40%                                                   ethylene glycol         10%                                                   nonylphenol polyethylene glycol ether                                                                  6%                                                   (15 mol EO)                                                                   sodium ligninsulfonate  10%                                                   carboxymethyl cellulose  1%                                                   37% aqueous solution of 0.2%                                                  formaldehyde                                                                  silicone oil in the form of a 75%                                                                     0.8%                                                  aqueous emulsion                                                              water                   32%                                                   ______________________________________                                    

The finely ground compound is intimately mixed with the adjuvants togive a suspension concentrate from which suspensions of any desiredconcentration can be prepared by dilution with water.

Biological Examples

In the following Examples B1 to B13, the compounds of the invention arevery effective against fungal attack.

Example B1

Action against Phytophthora infestans on tomatoes

a) Curative action

After a cultivation period of 3 weeks, tomato plants of the "Roter Gnom"variety are sprayed with a zoospore suspension of the fungus andincubated in a humidity chamber at 18°-20° C. and saturated atmospherichumidity. Wetting is discontinued after 24 hours. After the plants havedried, they are sprayed with a mixture prepared from a wettable powderformulation of the test compound in a concentration of 200 ppm. Afterthe spray coating has dried, the plants are put back into the climaticchamber for 4 days. The number and size of the typical leaf specksoccurring after this time serve as indicators for determining theefficacy of the test compounds.

b) Preventive-systemic action

A wettable powder formulation of the test compound is applied in aconcentration of 600 ppm (based on the volume of the soil) to thesurface of the soil of 3-week-old tomato plants of the "Roter Gnom"variety. After a waiting time of 3 weeks, the underside of the leaves ofthe plants is sprayed with a zoospore suspension of Phytophthorainfestans. The plants are then kept for 5 days in a spray chamber at18°-20° C. and saturated atmospheric humidity. The number and size ofthe typical leaf specks occurring after this time serve as indicatorsfor determining the efficacy of the test compounds.

Whereas infestation is 100% on untreated and infected control plants,infestation in both tests is reduced to 20% or less with compounds ofTables 1, 2 or 3, especially with compounds 1.1, 1.3, 1.6, 1.14, 1.22and 1.41 (0-5% infestation).

Example B2

Action against Plasmopara viticola (Bert. et Curt) (Berl. et DeToni) onvines

a) Residual preventive action

Vine cuttings of the Chasselas variety are reared in a greenhouse. Threeplants in the 10-leaf stage are sprayed with a spray mixture formulation(200 ppm a.i.) of the test compound. After the spray coating has dried,the plants are infected uniformly on the underside of the leaves with aspore suspension of the fungus. The plants are then kept in a humiditychamber for 8 days, after which time marked symptoms of disease areobserved on the control plants. The number and size of the infectedareas on the untreated plants act as an indicator of the efficacy of thetested compounds.

b) Curative action

Vine cuttings of the Chasselas variety are reared in a greenhouse andsprayed in the 10-leaf stage on the underside of the leaves with a sporesuspension of Plasmopara viticola. After 24 hours in the humiditychamber, the plants are sprayed with a spray mixture (200 ppm) of thetest compound. The plants are then kept for another 7 days in thehumidity chamber. After this time the control plants exhibit symptoms ofthe disease. The number and size of the infected areas on the untreatedplants act as an indicator of the efficacy of the tested compounds.

Compared with the control plants, infestation on the plants treated withcompounds of formula I is 20% or less. Plants treated with compounds1.4, 1.5, 1.13, 1.41, 1.52 and 1.67 exhibit virtually no infestation.

Example B3

Action against Pythium debaryanum on sugarbeet (Beta vulgaris)

a) Action after soil application

The fungus is cultivated on sterile oat grains and added to a mixture ofsoil and sand. Flowerpots are filled with the infected soil in whichsugarbeet seeds are then sown. Immediately after sowing, an aqueoussuspension (20 ppm a.i., based on the volume of the earth) prepared froma wettable powder formulation of the test compound is poured over thesoil. The pots are then stood in a greenhouse at 20°-24° C. for 2-3weeks. The soil is kept uniformly moist by continual light spraying withwater. Evaluation of the test is made by observing the emergence of thesugarbeet plants and counting the number of healthy and diseased plants.

b) Action after dressing application

The fungus is cultivated on sterile oat grains and added to a mixture ofsoil and sand. Flowerpots are filled with the infected soil in whichsugarbeet seeds are sown that have been dressed with a dressing powderformulation of the test compound (1000 ppm a.i., based on the weight ofthe seeds). The pots are then stood in a greenhouse at 20°-24° C. for2-3 weeks. The soil is kept uniformly moist by lightly spraying it withwater. Evaluation of the test is made by observing the emergence of thesugarbeet plants and counting the number of healthy and diseased plants.

After treatment with compounds of formula I, more than 80% of the plantsemerge. In the pots, only isolated plants of unhealthy appearance areobserved.

Example B4

Residual-protective action against Cercospora arachidicola on groundnutplants

Groundnut plants 10-15 cm in height are sprayed to drip point with anaqueous spray mixture (0.02 ppm a.i.) of the test compound and infected48 hours later with a conidia suspension of the fungus. The infectedplants are incubated for 72 hours at c. 21° C. and high humidity andthen stood in a greenhouse until the typical leaf specks occur.Evaluation of the fungicidal action is made 12 days after infection andis based on the number and size of the specks.

Compounds of formula I reduce the leaf specks to below c. 10% of theleaf surface. In some cases, infestation is reduced to 0-5% (compounds1.1, 1.3, 1.4, 1.5, 1.6, 1.9, 1.22, 1.40, 1.41, 1.52, 1.62, 1.63, 1.67).

Example B5

Action against Puccinia graminis on wheat

a) Residual-protective action

Wheat plants are sprayed to drip point 6 days after sowing with anaqueous spray mixture (0.02% a.i.) of the test compound and infected 24hours later with a uredospore suspension of the fungus. After anincubation time of 48 hours (conditions: 95-100% relative humidity at20° C.), the plants are stood at 22° C. in a greenhouse. Evaluation ofthe rust pustule development is made 12 days after infection.

b) Systemic action

Wheat plants are drenched 5 days after sowing with an aqueous spraymixture of the test compound (0.006% a.i., based on the volume of thesoil). Care is taken that the spray mixture does not come in contactwith the growing parts of plants. After 48 hours, the plants areinfected with a uredospore suspension of the fungus. After an incubationperiod of 48 hours (conditions: 95-100% relative humidity at 20° C.),the plants are stood at 22° C. in a greenhouse. Evaluation of the rustpustule development is made 12 days after infection (compounds 1.1, 1.3and others).

Compounds of formula I, especially those of Table 1, effect a markedreduction of fungus infestation, in some eases to 10-0%: compounds 1.1,1.3, 1.5, 1.6, 1.13, 1.28, 1.58, 1.67.

Example B6

Action against Pyricularia oryzae on rice plants

a) Residual-protective action

After a cultivation period of 2 weeks, rice plants are sprayed to drippoint with an aqueous spray mixture (0.02 ppm a.i.) of the testcompound. After 48 hours the treated plants are infected with a conidiasuspension of the fungus. Evaluation of fungus attack is made 5 daysafter infection, while maintaining conditions of 95-100% relativehumidity and 22° C.

b) Systemic action

2-week-old rice plants are drenched with a spray mixture of the testcompound (0.006% a.i., based on the volume of the soil), while ensuringthat the spray mixture does not come in contact with the growing partsof plants. The pots are then filled with water until the lowermost partsof the rice stalks are standing in water. After 96 hours the treatedrice plants are infected with a conidia suspension of the fungus. Fungusinfestation is evaluated after incubating the infected plants for 5 daysat 95-100% relative humidity and c. 24° C.

Compounds of formula I substantially inhibit the outbreak of the diseaseon the infected plants, e.g. compounds 1.4, 1.5, 1.20, 1.28, 1.52, 1.67.

Example B7

Action against Erysiphe graminis on barley

a) Residual protective action

Barley plants about 8 cm in height are sprayed to drip point with aspray mixture (0.02% a.i.) of the test compound and the treated plantsare dusted with conidia of the fungus 3 to 4 hours later. The infectedplants are stood in a greenhouse at c. 22° C. and fungus infestation isevaluated 10 days after infection.

b) Systemic action

Barley plants about 8 cm in height are drenched with an aqueous spraymixture (0.002% a.i., based on the volume of the soil) prepared from awettable powder formulation of the test compound. Care is taken that thespray mixture does not come in contact with the growing pans of theplants. The treated plants are dusted 48 hours later with conidia of thefungus. The infected plants are then stood in a greenhouse at c. 22° C.and evaluation of infestation is made 10 days after infection.

Compounds of formula I are substantially able to reduce infestation toless than 20%, and in some cases also almost completely (compounds 1.1,1.5, 1.12, 1.13, 1.22, 1.33, 1.58, 1.63, 1.67.

Example B8

Action against Podosphaera leucotricha on apple shoots

Residual-protective action

Apple cuttings with c. 15 cm fresh shoots are sprayed with a spraymixture (0.06% a.i.) of the test compound. The plants are infected 24hours later with a conidia suspension of the fungus and then stood in ahumidity chamber at 70% relative humidity at 20° C. Fungus infestationis evaluated 12 days after infection.

Compounds of formula I, e.g. compounds 1.1, 1.16 or 1.28, inhibitinfestation to less than 20%. Infestation of control plants is 100%.

Example B9

Action against Botrytis cinerea on apples

Residual-protective action

Artificially damaged applies are treated by dropping a spray mixture(0.02% a.i.) of the test compound on to the injury sites. The treatedfruit is then inoculated with a spore suspension of the fungus andincubated for 1 week at high humidity and c. 20° C. The fungicidalaction of the test compound is determined from the number of injurysites attacked by rot. Some of the compounds of formula I of Table 1, 2or 3 are able to inhibit rot completely, e.g. compounds 1.28, 1.61 and1.62.

Example B10

Action against Helminthosporium gramineum

Wheat grains are contaminated with a spore suspension of the fungus andleft to dry. The contaminated grains are dressed with a suspension ofthe test compound (600 ppm a.i., based on the weight of the seeds). Twodays later the grains are laid out on agar dishes and development of thefungus colonies around the grains is assessed after 4 days. Evaluationof the test compound is made by assessing the number and size of thecolonies. Compounds 1.1, 1.28 and 1.4 1 effected complete inhibition.

Example B11

Action against Colletotrichum lagenarium on cucumbers

After a cultivation period of 2 weeks, cucumber plants are sprayed witha spray mixture (concentration: 0.002%) of the test compound. Two dayslater the plants are infected with a spore suspension (1.5×10⁵spores/ml) of the fungus and incubated for 36 hours at 23° C. and highhumidity. Incubation is then continued at normal humidity and c. 22°-23°C. Fungal infestation is evaluated 8 days after infection. Infestationof untreated and infected control plants is 100%.

Some of the compounds of formula I inhibit infestation almostcompletely, e.g. compounds 1.1, 1.5, 1.13, 1.15, 1.20, 1.22, 1.52, 1.65.

Example B12

Residual protective action against Venturia inaequalis on apple shoots

Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spraymixture (0.006% a.i.) prepared from a wettable powder formulation of thetest compound. The plants are infected 24 hours later with a conidiasuspension of the fungus. The plants are then incubated for 5 days at90-100% relative humidity and stood in a greenhouse for a further 10days at 20°-24° C. Scab infestation is evaluated 15 days afterinfection.

Compounds of Tables 1-3 are very effective against Venturia (infestationless than 20%). Thus compounds 1.1, 1.3, 1.5, 1.13, 1.14, 1.15, 1.41,1.52 reduce Venturia infestation to 0-5%. Venturia infestation onuntreated, infected shoots is 100%.

Example B13

Action against Rhizoctonia solani (soil fungus on rice plants)

a) Protective-local soil application

12-day-old rice plants are drenched with a spray mixture prepared from aformulation of the test compound (20 ppm a.i.) without wetting thegrowing pans of the plants. A suspension of mycelium and sclerotia of R.solani is applied to the surface of the soil to infect the treatedplants. The plants are incubated for 6 days at 27° C. (day) and 23° C.(night) and 100% relative humidity (humidity box) in a climatic chamberand then evaluation is made of the fungus infestation on the leafsheath, leaves and stems.

b) Protective-local foliar application

12-day-old rice plants are sprayed with spray mixture prepared from aformulation of the test compound. The treated plants are infected oneday later with a suspension of mycelium and sclerotia of R. solani. Theplants are incubated for 6 days at 27° C. (day) and 23° C. (night) and100% relative humidity (humidity box) in a climatic chamber and thenevaluation is made of the fungus infestation on the leaf sheath, leavesand stems.

Compounds of Tables 1-3 exhibit good activity by inhibiting Rhizoctoniainfestation. Thus compounds 1.1, 1.3, .1.4, 1.6, 1.9 und 1.28 inhibitfungus infestation to 0-5%. In contradistinction thereto, infestation is100% on untreated and infected plants.

What is claimed is:
 1. A compound of formula I ##STR14## wherein R₁ ishydrogen or methyl,R₂ is hydrogen, halogen, OCH₃, SCH₃ or CN, R₃, R₄, R₅are each independently of one another hydrogen, halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy, C₂ -C₅ alkoxycarbonyl, C₁ -C₅ alkanoyl, C₁ -C₄ haloalkyl,C₁ -C₄ haloalkoxy, CN, NO₂, or wherein two of these substituents areadjacent to each other and together are a methylenedioxy ordifluoromethylenedioxy radical, K, L, M are each nitrogen, and Y isoxygen or sulfur.
 2. A compound according to claim 1, wherein R₁, R₂, K,L, M and Y have the given meanings and R₃, R₄, R₅ are each independentlyof one another hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkyl, C₁ -C₄ haloalkoxy, CN, NO₂, or wherein two of thesesubstituents are adjacent to each other and together are amethylenedioxy or difluoromethylenedioxy radical.
 3. A compoundaccording to claim 1, wherein R₁ is methyl, R₄ is hydrogen, and Y isoxygen.
 4. A compound according to claim 3, wherein R₂ is fluoro,chloro, bromo, OCH₃, SCH₃ or CN, and R₃ and R₅ are each independently ofthe other hydrogen, halogen, methyl, ethyl, methoxy, ethoxy, CF₃, OCF₃,OCHF₂, NO₂ or CN, or both adjacent to each other are a methylenedioxy ordifluoromethylenedioxy radical.
 5. A microbicidal composition comprisingas active ingredient a compound of formula I according to claim 1,together with an inert carrier.
 6. A process for controlling plantdiseases and for preventing infestation by microorganisms by applicationof a fungicidally effective amount of a compound of formula I as claimedin claim 1 to plants, to parts thereof or to the locus thereof.